WO2003078525A1

WO2003078525A1 - Flame-retardant aromatic polycarbonate resin composition

Info

Publication number: WO2003078525A1
Application number: PCT/JP2002/013404
Authority: WO
Inventors: Akira Miyamoto; Toshiharu Sakuma; Kazuhiro Shibuya
Original assignee: Asahi Kasei Chemicals Corporation
Priority date: 2002-03-18
Filing date: 2002-12-20
Publication date: 2003-09-25
Also published as: CN1649713A; JPWO2003078130A1; DE10297672B4; AU2002357505A1; KR100621390B1; TWI248960B; US20050256227A1; CN100431820C; US20050159518A1; KR100656722B1; TW583269B; AU2003220908A1; JP4236002B2; DE10297672T5; US7060780B2; WO2003078130A1; DE10392418B4; DE10392418T5; KR20040097183A; TW200305612A

Abstract

A flame-retardant aromatic polycarbonate resin composition which comprises 100 parts by weight of an aromatic polycarbonate (A), 0.01 to 0.5 parts by weight of metal oxide particles having a branched structure (metal oxide particle aggregates and/or metal oxide particle agglomerates) (B), 0.0001 to 0.2 parts by weight of an alkali metal salt of an organic sulfonic acid (C), and 0.01 to 0.5 parts by weight of a fluoropolymer (D), characterized in that the metal oxide particles (B) have been dispersed in a mixture of the aromatic polycarbonate (A), metal oxide particles (B), and organic sulfonic acid alkali metal salt (C) and at least 70% of the metal oxide particles (B) have a particle diameter in the range of 10 to 200 nm.

Description

Description Flame retardant aromatic polycarbonate resin composition Technical field

The present invention relates to a flame-retardant aromatic polycarbonate resin composition. More specifically, the present invention relates to an aromatic polycarbonate

(A), a specific amount of aggregated metal oxide particles having a branched structure and Z or metal oxide particles that are agglomerated metal oxide particles (B), a specific amount of an alkali metal salt of an organic sulfonic acid (C) And an aromatic polycarbonate resin composition comprising a specific amount of a fluoropolymer (D), wherein the metal oxide particles (B) are composed of the components (A), (B) and (C) being dispersed in the mixture, wherein at least 70% of the metal oxide particles (B) have a particle diameter in the range of 10 to 200 nm. The present invention relates to a flame-retardant aromatic polycarbonate resin composition which is excellent in flame retardancy without using a bromine-based flame retardant or a phosphorus-based flame retardant. Exhibits heat resistance and impairs the inherent heat resistance and impact resistance of aromatic polycarbonate And without exhibits excellent melt stability. Prior art

The flame-retardant aromatic polycarbonate resin composition is Monitors, notebook computers, copiers, facsimiles, printers, projectors, portable equipment, electronics, electrical equipment, precision machinery, etc. Widely used as molding material for

In recent years, the thickness of various products using an aromatic polycarbonate resin composition has been tending to be thinner in order to reduce the weight, and more sophisticated from the viewpoint of fire safety. Flame retardant performance is required.

The bromine-based flame retardants used in the prior art and the aromatic polycarbonate resin compositions flame-retarded by the use of phosphorus-based flame retardants or silicone-based flame retardants Due to the insufficient thermal stability of the resin itself, molding at a high molten resin temperature will increase the thermal decomposition of the resin composition and reduce the properties of the resin composition There was a problem. '' Therefore, in order to improve the moldability at the melting resin temperature where the decomposition of the resin composition does not occur, it is necessary to use an aromatic polystyrene resin and acrylonitrile. As is typified by alloys such as ABS resin, a method of blending other resins with aromatic polycarbonate is proposed as a technique to improve the balance between melt fluidity and flame retardancy. It has been put to practical use.

However, the method of blending another resin with the aromatic polycarbonate has a problem that the properties inherent to the aromatic polycarbonate, such as heat resistance and impact resistance, are impaired. In addition, in recent years, from the viewpoint of environmental protection, there has been a strong demand for the development of low-impact, flame-retardant aromatic poly-carbonate resin compositions that do not use brominated or phosphorus-based flame retardants. ing.

As a method to improve the flame retardancy of aromatic polycarbonates without using brominated or phosphorus-based flame retardants, Japan's Special Publication No.

No. 6,038,418 (corresponding to U.S. Pat. No. 4,391,935) states that aromatic polycarbonates can be treated with organic alkali metal salts or alkaline earth metal salts. Compositions comprising polytetrafluoroethylene are disclosed.

However, in the aromatic polycarbonate composition disclosed in the publication, an organic alkali metal salt or an alkaline earth metal salt and a polytetratene are required to exhibit excellent flame retardancy in a thin-walled molded product. It is necessary to increase the amount of lafluoroethylene, which causes a problem that the melt stability of the composition is insufficient.

Further, Japanese Patent Application Laid-Open No. 2000-27083 discloses a method in which an organic siloxane compound, a fluorine-containing compound, and an organic alkali metal salt are added to an aromatic polycarbonate. Although a composition is disclosed, the aromatic polyester composition disclosed in the publication has insufficient melt stability of the organic siloxane compound due to insufficient thermal stability. is there.

In Japanese Patent Application Laid-Open No. 2000-1402, the aromatic polystyrene resin contains core shell type rubber and fluorine. Although a composition obtained by adding a compound and an organic alkali metal salt is disclosed, the aromatic polycarbonate composition disclosed in the publication has insufficient heat stability of the core-shell type rubber. Therefore, the melt stability of the composition is also insufficient.

On the other hand, there has been proposed a method for improving flame retardancy by blending inorganic compound fine particles having a size on the order of nanometers with aromatic polycarbonate.

Japanese Patent Application Laid-Open No. 53-256660 discloses a method of incorporating an inorganic fine powder having an average particle diameter of 100 nm or less into a flame-retarded synthetic resin. Since brominated flame retardants and phosphorus-based flame retardants are used, they are not only environmentally unfavorable, but also have an insufficient effect of preventing dripping of combustion substances in thin-walled molded products.

International Publication (W〇) No. 0 ◦Z334371 discloses that flame retardant polycarbonate has an average particle diameter of 1 nrr! Although a method of blending silicon compound particles of up to 20 m is disclosed, the examples of the publication use a phosphorus-based flame retardant, which is not only environmentally unfriendly but also aromatic. There is a problem in that the properties inherent in poly-polypropylene are impaired, for example, heat resistance and impact resistance.

U.S. Pat.No. 5,274,0117, W〇-No. 0Z550111, Japanese Patent Publication No. 2000-150200, Japanese Patent Publication In the publication No. 200-600, the thermoplastic resin Techniques for blending an inorganic compound having a fine particle size are disclosed. However, the resin compositions disclosed in these publications have insufficient flame retardancy in the case of a thin molded article, or have a low melt stability. There is a problem of insufficiency.

In other words, the flame retardant aromatic polycarbonate based on the prior art is insufficient in the thermal stability of the flame retardant used, and the flame retardant must be used in order to exhibit high flame retardancy. There was a problem that the melt stability was insufficient due to reasons such as the need to increase the amount used, and the physical properties of the product deteriorated.

Therefore, excellent flame retardancy is exhibited without using a brominated flame retardant or a phosphorus-based flame retardant, and excellent heat resistance without impairing the inherent heat resistance and impact resistance of aromatic polycarbonate. It has been desired to develop an aromatic polycarbonate resin composition exhibiting melt stability. · Summary of the Invention

Under such circumstances, the present inventors have intensively studied to achieve the above object. As a result, the aromatic polycarbonate (A), a specific amount of metal oxide aggregated particles having a branched structure and / or metal oxide agglomerate particles (B), Amount of an aromatic metal salt of an organic sulfonic acid (C) and a specified amount of a fluoropolymer (D) A carbonate resin composition, wherein the metal oxide particles (B) are dispersed in a mixture of the components (A), (B) and (C), and the metal oxide particles (B) A flame retardant aromatic polycarbonate resin composition characterized in that at least 70% of the resin has a particle diameter in the range of 10 to 200 nm. Found to exhibit excellent flame retardancy without using a flame retardant, and exhibit excellent melt stability without impairing the heat resistance and impact resistance inherent to aromatic polycarbonate. Was. Based on this finding, the present invention has been completed.

Therefore, one of the main objects of the present invention is to exhibit excellent flame retardancy without using a brominated flame retardant or a phosphorus-based flame retardant, and to have the heat resistance inherent to the aromatic polycarbonate and the impact resistance. An object of the present invention is to provide a flame-retardant aromatic polyether-Polynate resin composition exhibiting excellent melt stability without impairing the composition.

The above and other objects, features and advantages of the present invention will become apparent from the following detailed description and the scope of the claims with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE FIGURES

Figure 1 shows the same procedure as in Example 4 except that the component (C) was changed to potassium perfluorosulfonate sulphonic acid salt (product name: "RM-65j") manufactured by Miteni, Italy. Obtained by molding the flame-retardant aromatic polyphenol resin composition obtained by the method of 3404

7 A 1/16 inch thick test specimen was subjected to a 20 mm vertical burn test.After the second 10 second flame contact in the 20 mm vertical burn test, the test specimen The fire extinguished by self-extinguishing (flammability was judged to be V-0)], and a photomicrograph of the surface of the test piece taken with a scanning probe microscope. [In the figure, the black portions indicate metal with a branched structure. Oxide particles (B), the remainder being aromatic polycarbonate (A), alkali metal salts of organic sulfonic acids

(C) and a fluoropolymer (D). In addition, in the micrograph of FIG. 1, the surface occupied area of the component (B) is 56%.]

Figure 2 shows another test specimen of 1 Z 16 inches thick obtained using the same composition as described above in connection with Figure 1 after being subjected to a 20 mm vertical burn test. [After the second 10 second flame contact in the 20 mm vertical burn test, the specimen extinguished itself in 6 seconds.

(The flame retardancy was judged to be V-0.)] Is a photomicrograph of the surface of the test piece taken through a scanning probe microscope. [In the figure, the black portions are metal oxides having a branched structure. Particles (B), and the remainder is a matrix consisting of an aromatic polysiloxane (A), an alkali metal salt of an organic sulfonic acid (C), and a fluoropolymer (D).] ,

FIG. 3 shows that a 1/16 inch thick test piece obtained by molding the aromatic polycarbonate resin composition obtained in Comparative Example 5 was subjected to a 20 mm vertical combustion test [ 20 mm vertical combustion test After the second 10 seconds of flame contact in the test, the test piece self-extinguished after a flame drip in 3 seconds (flammability was judged to be V-2)], and the surface of the test piece was scanned with a scanning probe. It is a microscope photograph taken through a microscope. DETAILED DESCRIPTION OF THE INVENTION

According to one embodiment of the present invention, 100 parts by weight of an aromatic polycarbonate (A)

A plurality of metal oxide particles having a branched structure (B) 0.01 to 0.5 parts by weight, provided that the plurality of metal oxide particles (B) are each independently a metal oxide having a branched structure Agglomerated particles or metal oxide agglomerated particles having a branched structure,

Alkali metal salt of organic sulfonic acid (C) 0.001 to 0.2 parts by weight, and

Fluoropolymer (D) 0.01 to 0.5 parts by weight

An aromatic polycarbonate resin composition comprising: the metal oxide particles (B), the aromatic polycarbonate (A), the metal oxide particles (B), and the organic resin. It is dispersed in a mixture of a sulfonic acid alkali metal salt (C),

At least 70% of the metal oxide particles (B) have a particle size in the range of 10 to 200 nm,

A flame-retardant aromatic polycarbonate resin composition characterized by this is provided. Next, in order to facilitate understanding of the present invention, first, basic features and preferred embodiments of the present invention will be listed.

1. Aromatic polycarbonate (A) 100 parts by weight,

Fluoropolymer (D) 0.01 to 0.5 parts by weight

An aromatic polycarbonate resin composition comprising: the metal oxide particles (B), the aromatic polycarbonate (A), the metal oxide particles (B), and the organic sulfonic acid. Alkali metal salt (C) dispersed in a mixture of

At least 70% of the metal oxide particles (B) have a particle size in the range of 10 to 20 nm;

Flame-retardant aromatic polyester resin composition characterized by this

2. The metal oxide particles (B) having a branched structure are particles of at least one metal oxide selected from silicon oxide, titanium oxide, and aluminum oxide. Aromatic Polypropylene resin composition described in the above.

3. The aromatic polycarbonate resin composition according to the above item 2, wherein the metal oxide particles (B) having a branched structure are silicon oxide particles produced by a dry method.

4. The aromatic polysiloxane according to any one of the above items 1 to 3, wherein the surface of the metal oxide particles (B) having a branched structure is modified with a silicon-containing compound. Fat composition.

5. The aromatic polycarbonate resin composition further comprises at least one additive selected from the group consisting of a reinforcing material and a filler.

(E) The aromatic polycarbonate resin composition according to any one of the above items 1 to 4, comprising 5 to 200 parts by weight.

6. The additive (E) is characterized in that it is at least one substance selected from the group consisting of glass fibers, carbon fibers, glass flakes, glass beads, glass balloons, quartz glass and silica. 6. The aromatic polycarbonate resin composition according to item 5, wherein

7. The aromatic polycarbonate (A) is characterized by being an aromatic polycarbonate obtained by a transesterification method. 3. The aromatic polycarbonate resin composition according to item 1 above.

Hereinafter, the present invention will be described in detail.

The aromatic polycarbonate which can be used as the component (A) of the present invention has a main chain composed of a repeating unit represented by the following formula (1).

-{~~ 0― Ar-1 0― C

0

(In the formula, Ar is a divalent aromatic group having 5 to 200 carbon atoms, for example, phenylene, naphthylene, pifenylene, or pyridylene, which are unsubstituted or substituted. It may be substituted, or also includes those represented by the following formula (2).)

—— Ar ¹ —— Y— Ar ² one (2)

(In the formula, Ar ¹ and Ar ² are each an arylene group. For example, they represent groups such as phenylene, naphthylene, biphenylene, and pyridylene, which are unsubstituted or substituted. And Y is an alkylene group or a substituted alkylene group represented by the following formula (3).)

(Wherein, RR ² , R ³ and R ⁴ are each independently a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, and a lower alkyl group having 5 to 10 carbon atoms. Aryl group, an aralkyl group having 7 to 31 carbon atoms, which may be optionally substituted by a nitrogen atom, a halogen atom, or an alkoxy group having 1 to 10 carbon atoms, and k is 3 to 1 R ⁵ and R ⁶ are individually selected for each X, and each is independently a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 30 carbon atoms. And optionally substituted by a halogen atom or an alkoxy group having 1 to 10 carbon atoms, and X represents a carbon atom.)

Further, a divalent aromatic group represented by the following formula (4) may be contained as a copolymer component.

-Ar ¹ — Z—Ar ² (4)

(Wherein, A r ¹ and A r ² are the same as those in the above formula (2). Z is a single bond or —〇, 1 C, 1 S—, _S 0 ₂ —, —CO . one, - CON (R ¹⁾ one (R ¹ is the formula and (3) the It is a divalent group such as )

Specific examples of the divalent aromatic group represented by the above formula (2) include those represented by the following.

I

SZS8.0 / C0 OAV Four

Fifteen

(Wherein R ⁷ and R ⁸ are each independently hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or Is an aryl group of the formulas 6 to 30. m and n are integers of 1 to 4, and when m is 2 to 4, each R ⁷ may be the same or different, and n is 2 In the case of to 4, each R ⁸ may be the same or different.)

Specific examples of the divalent aromatic group represented by the above formula (4) include those represented by the following.

as well as

CH ₃ CH, (In the formula, R ⁷ , R ⁸ , m and n are as described above.) Among them, a compound represented by the following formula (5) is a preferable example.

In particular, an aromatic polycarbonate containing 85 mol% or more (based on one unit of all monomers in the aromatic polycarbonate) of a repeating unit represented by the above formula (5) as Ar is particularly preferable. preferable.

Further, the aromatic polycarbonate that can be used in the present invention may have a branched structure having a trivalent or higher aromatic group as a branch point.

Although the molecular structure of the polymer terminal is not particularly limited, at least one terminal group selected from a phenol group, an aryl carbonate group, and an alkyl group can be bonded. The aryl carbonate terminal group is represented by the following formula (6).

-0—— C—— 0—— Ar ³ (6)

II

0 (In the formula, Ar ³ is a monovalent aromatic group having 6 to 30 carbon atoms, and the aromatic ring may be substituted.)

Specific examples of aryl carbonate terminal groups include, for example, those represented by the following formula.

■ 0——

-0

• 0

The terminal group of the alkyl group is represented by the following formula (7).

-0— C—— 0—— R9 (7)

0 (In the formula, ⁹ represents a straight-chain or branched alkyl group having 1 to 20 carbon atoms.)

Specific examples of the alkyl carbonate terminal group include, for example, those represented by the following formula.

-0— C— 0— C ₈ H ₁₇ , — 0— — 0— C 12 ^H 25, and

• o- c- -ο— c 18 ^Η 3 7

ϋ

Of these, a phenol group, a phenyl carbonate group, a ρ-t-butylphenyl carbonate group, a p-cumylphenyl carbonate, and the like are preferably used.

In the present invention, the ratio of the phenol group terminal to the other terminal is not particularly limited, but from the viewpoint of exhibiting excellent flame retardancy and melt stability in the resin composition in a good balance. The ratio of the phenol group terminals is preferably in the range of 5 to 70% of the total number of terminal groups, more preferably in the range of 10 to 50%.

Generally, the phenol group terminal amount is measured by NMR (NMR method), by titanium (titanium method), or by UV or IR. (UV method or IR method), but in the present invention, it was determined by NMR method.

The weight average molecular weight (Mw) of the aromatic polycarbonate (A) used in the present invention is usually from 5,000 to 500,000, preferably from 10,000 to 10,000. 100,000, more preferably 13,500 to 500,000, even more preferably 15,500 to 30,000, Particularly preferably 180

0 25, 00 00, most preferably 20, 00 00 to 23

0 0 0.

It is also a preferred embodiment that the aromatic polycarbonate (A) used in the present invention is a combination of two or more aromatic polycarbonates having different molecular weights. For example, Mw is usually in the range of 14 000 to 16 000, and aromatic polycrystalline polycarbonate of the optical disk material, and Mw is usually 20000 to 50, Aromatic polycarbonates for injection molding or extrusion molding in the range of 0.000 may be used in combination.

In the present invention, the measurement of the weight average molecular weight (M w) of the aromatic polycarbonate is performed using a gel “permeation” chromatograph (GPC), and the measurement conditions are as follows. That is, it can be obtained from a polystyrene gel using tetrahydrofuran as a solvent, and a calibration curve of reduced molecular weight from the constitution curve of standard monodisperse polystyrene according to the following equation. M 8

p c = 0. 3 5 9 1 M 0 3 8

p s

(M _PC molecular weight of the aromatic poly force one Pone DOO, M _PS molecular weight of the poly scan styrene)

As the aromatic polycarbonate used in the present invention, those produced by a known method can be used. Specifically, a known method for reacting an aromatic dihydroxy compound with a carbonate precursor, for example, converting an aromatic dihydroxy compound and a carbonate precursor (for example, phosgene) into sodium hydroxide. Interfacial polymerization method (for example, phosgene method) in which an aqueous solution and a methylene chloride solvent are used for reaction, and ester exchange method (for melting an aromatic dihydroxy compound and a diester carbonate (for example, diphenyl alcohol)). ), A method of solid-phase polymerization of a crystallized carbonate prepolymer obtained by the phosgene method or the melting method (Japanese Patent Application Laid-Open No. 1-158033 (US Pat. No. 1), Japanese Patent Application Laid-Open No. Hei 1 — 2 7 1 4 2 6, Japanese Patent Laid-Open No. Hei 3 — 688627 (corresponding to US Pat. No. 5,204, 377)) Can be used. Preferred aromatic polycarbonates include aromatic chlorine-free aromatic compounds produced by ester exchange from divalent phenol (aromatic dihydroxy compound) and carbonic acid diester. You can give a bonus.

In the phosgene method, for example, US Pat. No. 4,736,013 On the other hand, transesterification methods such as the melting method and the solid-phase polymerization method adjust the molar ratio of the aromatic dihydroxy compound and diphenyl carbonate, and use the method described in the official gazette. It can be adjusted by the method described in JP-A-88862.

In the present invention, it is preferable that the aromatic polycarbonate (A) is an aromatic polycarbonate having a branched structure in the main chain in order to improve the melt fluidity. As a method of obtaining such an aromatic polycarbonate having a branched structure, a method of adding a trivalent or higher polyhydric hydroxy compound as a copolymerization component to produce it, for example, US Pat. There are also methods disclosed in Japanese Patent Publications Nos. 677, 162, 4, 562, 242, and German Patents 3, 149, 812, etc. Particularly preferred aromatic polycarbonates having a branched structure which can be used in the present invention can be produced by the method described in US Pat. No. 5,932,683.

Particularly, in the present invention, the following formula (8),

(In the formula, Ar ′ represents a trivalent aromatic group having 5 to 200 carbon atoms, and X represents a polycarbonate chain composed of a repeating unit represented by the formula (1).)

The unit having a branched structure shown below (hereinafter referred to as “heterogeneous bond unit”) is preferably in the range of 0.01 to 0.5 mol%, and more preferably in the range of 0.03 to 0.3 mol%. %, More preferably in the range of 0.4 to 0.2 mol%, particularly preferably in the range of 0.05 to 0.1 mol%. It is preferable for obtaining a resin composition having an excellent balance between flame retardancy and melt fluidity.

Preferred examples of the aromatic polycarbonate used in the present invention include the following formula (9):

And the following unit (10)

(Wherein, X represents a molecular chain containing a unit represented by the formula (9)), and the amount of the heterogeneous binding unit is preferably 0.01 to 0. In the range of 0.5 mol%, more preferably from 0.3 to 0.3 mol%, more preferably from 0.44 to 0.2 mol%, particularly preferably from 0.05 to 0.5 mol%. ~ 0.1 mol% aromatic polycarbonate.

The component (B) in the present invention is a metal oxide particle having a branched structure.

In the present invention, the term “metal oxide particles having a branched structure” refers to aggregated particles in which primary particles of a metal oxide are bonded in a branched chain. (aggregate) and / or agglomerate particles. In the present invention, “particles” refers to a force for observing an ultrathin section of a resin composition using a transmission electron microscope (TEM) or a molded article of the resin composition using a scanning probe atomic force microscope (SPM). When observed on the surface or cut surface (TEM and SPM observations are usually performed at 10,000 to 100,000 times), it means those that are observed as independent particles. The metal oxide particles (B) used in the present invention are, as described above, aggregates, and Z or agglomerate particles, but as independent particles when observed by the above method. To be observed.

In the present invention, the particle size of the metal oxide particles (B) having a branched structure is measured by observation with the above-mentioned transmission electron microscope (TEM) or observation with a scanning probe atomic force microscope (SPM). be able to. That is, a photograph is taken in the above-described microscopic observation, and the particle diameter of each of 100 or more particles in the resin composition is measured from the obtained micrograph. In addition, determine the particle size distribution. For the particle diameter, the area S of the particle is determined, and (4S / 7C) ° · ⁵ is used as the particle diameter using S.

Examples of the metal oxide particles having a branched structure (Β) include, for example, silicon oxide and titanium oxide in the form of aggregated or agglomerated particles in which primary particles of a metal oxide are bonded in a branched chain. Aluminum oxide, zinc oxide, cerium oxide, and oxide 13404

Examples include 25 um, zirconium oxide, tin oxide, iron oxide, magnesium oxide, manganese oxide, and holmium oxide.

Among the above, particles of silicon oxide, titanium oxide and aluminum oxide having a branched structure are preferred, and silicon oxide particles having a branched structure are particularly preferred.

In the resin composition of the present invention, at least 70% of the metal oxide particles (B) are in the range of 10 to 200 nm in order to exhibit high flame retardancy and excellent impact resistance. It is necessary that the particle diameter be within the above range, preferably 75% or more, more preferably 80% or more, and particularly preferably 90% or more. The number average particle diameter of the metal oxide particles (B) is usually from 30 to 25 O nm, preferably from 40 to 20 O nm, and more preferably from 50 to: L 5 O nm. nm.

Further, the metal oxide particles (B) preferably have a specific surface area of 50 to 400 m ² Zg, as determined by the BET method using nitrogen gas adsorption, and 100 to 350 m ² More preferably, it is Z g, and even more preferably, it is 150 to 300 m ² / g.

The component (B) preferably used in the present invention is a silicon oxide particle having a branched structure, and is obtained by hydrolyzing a volatile silicon compound such as a silicon halide in a oxyhydrogen flame at a high temperature. Silicon oxide particles obtained by the so-called “dry method” that synthesizes silicon oxide Can be used particularly favorably. Silicon oxide having a branched structure obtained by such a dry method is generally referred to as "fumed silica".

Such a fumed silica can be produced, for example, by the method described in Japanese Patent Application Laid-Open No. 2000-82627. As a specific production example, a volatile silicon compound is used as a raw material, and is supplied to a burner together with a combustible gas and a mixed gas containing oxygen, and is burned in a flame of 1,000 to 2,1,100. An example is a method of thermal decomposition at a high temperature of 00 ° C. Is a volatile silicon compound as a raw material in here, for _{example, S i H 4, S i} C l 4, CH 3 S i C l 3, CH 3 S i HC l 2, HS i C l 3, _{_{(CH 3) 2 S i C}} l 2, (CH 3) 3 S i C 1, (CH 3) 2 S i H 2, (CH 3) 3 S i H, and the arc alkoxysilane emissions and the like are exemplified can, inter alia _{S i C i 4, CH 3} S i C 1 3, CH 3 S i HC l 2, HS i C l "(CH 3) 2 S i C 1 2, (CH 3) 3 S i C Preferred is a silicon halide compound such as 1. In addition, the combustible gas and the mixed gas containing oxygen are preferably those that can generate water, and hydrogen, methane, butane, and the like are suitable. Oxygen, air, etc. are used as the oxygen-containing gas.

The molar ratio of the volatile silicon compound to the mixed gas is such that the molar equivalent of the volatile silicon compound is 1 molar equivalent, and the molar equivalent of oxygen in the mixed gas containing oxygen and flammable gas, hydrogen, is 2.5 to 3. 5 and the molar equivalents of hydrogen should be adjusted in the range of 1.5 to 3.5. Is preferred. Here, the molar equivalents of oxygen and hydrogen represent stoichiometric equivalents that react with each raw material compound (volatile silicon compound). When a hydrocarbon fuel such as methane is used, the molar equivalent in terms of hydrogen shall be expressed. In this method, the average primary particle diameter of silica can be reduced by using an excess amount of hydrogen and oxygen with respect to 1 mol of a volatile silicon compound, so that the solid (silica) in the reaction mixture is reduced. This can be achieved by reducing the ratio of / gas (oxygen, hydrogen), thereby reducing collisions between solid particles and suppressing particle growth due to melting.

When the surface of the component (B) used in the present invention is surface-modified with a silicon-containing compound, the component (B) can be prevented from agglomerating in the resin composition and can be dispersed well. , Preferred.

Here, “surface modification” includes surface modification through a covalent bond, and surface modification by Z or Van der Waals force or hydrogen bond, but preferably the former surface modification through a covalent bond. You.

The silicon-containing compound is at least one selected from the group consisting of chlorosilane, alkoxysilane, hydrosilane, silylamine, silane coupling agent, and polyorganosiloxane. Is a silicon-containing compound.

The chlorosilane refers to a silicon-containing compound containing 1 to 4 chlorine atoms in a molecule, and is, for example, an alkyl having 1 to 12 carbon atoms. Rutrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyl trichlorosilane, diphenylchlorosilane, trifluorochlorosilane, trifluoropropyl Examples include chlorochlorosilane, hepclodecafluorodecyltrichlorosilane, and the like, with dimethyldichlorosilane, octyltrichlorosilane, and trimethylchlorosilane being preferred. Yes.

The alkoxysilane refers to a silicon-containing compound having 1 to 4 methoxy groups or ethoxy groups in the molecule, for example, tetramethoxysilane, C2-C12 alkyltrimethoxysilane. , Dimethyl methoxy silane, phenyl trimethoxy silane, diphenyl dimethoxy silane, tetraethoxy silane, methyl triethoxy silane, dimethyl ethoxy silane, phenyl triethoxy silane, diphenyl ethoxy silane , Hexyl triethoxysilan, trifluoropropyltrimethoxysilane, heptadecatrifluorodecyl trimethoxysilane, etc., and among them, methyltrimethoxysilane. Octyl trimethoxysilane, decyl trimethoxysilane Arbitrariness down, is Jimechirujime Tokishishira down preferred.

The term “hydrosilane” refers to a silicon-containing compound having 1 to 4 Si—H bonds in the molecule, and includes, for example, a C 1 to C 12 alkylsilane and a di (C 1 to C 12 alkyl). ) Silane, tri (C 1 -C 12 alkyl) silane, etc. Of these, octylsilane is preferred.

The silylamine is represented by the following general formula in the molecule:

≡ S i-N =

Represents a silicon-containing compound having a silylamine structure represented by, for example, hexamethyldisilazane, hexaphenyldisilazane, trimethylsilyldimethylamine, trimethylsilyldimethylamine, trimethylsilylamine Midazole and the like can be mentioned, and among them, hexamethyldisilazane is preferable. The silane coupling agent has the following general formula in the molecule: RS i Y _n X _m

(Where R is a functional group capable of binding to an organic material, for example, an organic substituent containing a vinyl group, a glycide group, a methyl group, an amino group, a mercapto group, etc. On the other hand, X is a hydrolyzable group capable of reacting with an inorganic material, for example, chlorine, an alkoxy group having 1 to 4 carbon atoms, and Y is an alkyl group having 1 to 4 carbon atoms. M is an integer of 1 to 3, n is an integer of 0 to 2, and m + n = 3.

Represents a silicon-containing compound represented by, and is a compound having a function of interposing an organic material and an inorganic material at the interface thereof and bonding them. Examples of the silane coupling agent include vinyl trichlorosilane, bieltrimethoxysilane, vinyltriethoxysilane, β- (3,4 epoxycyclohexyl) ethyl Remethoxysilan, τ — Glycidoxypropyl trimethoxy La down, § Guri sheet Dokishipuro Pirumechiruje Tokishishira _down, τ - glycinate Dokishipuro pill door Li et Tokishishira _down, τ Ichime Yuku Li Rokishipuro Pirumechirujime Tokishiran, Ryo one meta-click re-Loki Cipro pill door Li main Bok Thira down, τ - Methacryloxypropyl methyl methyl ethoxysilane, fermethacryloxypropyl triethoxysilane, Ν-β (aminoethyl) τ-aminopropylmethyl dimethoxysilane, Ν — (aminoethyl) r-7 minopropyl Limethoxysilane, N- / 3 (aminoethyl) T-amino propyl triethoxysilane, arnino propyl triethoxy silane, arnamino propyl triethoxysilane , N-phenylamine propyltrimethoxysilane Acrylpropyl pyrritol trimethoxysilane, r-mercaptopropyl trimethoxysilane, and the like, among which β- (3,4 epoxy-hexyl) ethyl trimethacrylate Toxicylane, τ-glycidoxypropyltrimethoxysilane,

7-Glycidoxypropylmethyl ethoxysilane, arg, and liquidoxypropyl triethoxysilane are preferred.

The polyorganosiloxane is a polymer of a silicon-containing compound, and examples thereof include oil, rubber, and resin-like polyorganosiloxanes. A 1,000 cSt silicone oil or a modified silicone oil can be preferably used.

As the silicone oil, dimethyl silicone oil, TJP02 / 13404

31 Examples include methylphenylsilicone oil and methylhydrogensilicone oil, with dimethylsilicone oil and methylphenylsilicone oil being particularly preferred.

The modified silicone oil may be at least one selected from the group consisting of an amino group, an epoxy group, a propyloxyl group, a hydroxyl group, a methacryl group, a mercapto group, and a phenol group in a molecule. Reactive silicone oil having one type of reactive substituent, polyether group, methylstyrene group, alkyl group, higher fatty acid ester group having 8 to 30 carbon atoms, and 1 to 30 carbon atoms A non-reactive silicone oil having at least one non-reactive substituent selected from the group consisting of an alkoxy group, a higher fatty acid group having 8 to 30 carbon atoms, and a fluorine atom. Hydroxy group-containing silicone oil, epoxy group-containing silicone oil, and polyether group-containing modified silicone oil are particularly preferred.

In the present invention, the surface treatment method relating to the component (B) is described, for example, in Japanese Patent Application Laid-Open Nos. 9-31027 and 9-59533 (US Pat. Nos. 5,843,52). No. 5), and the method described in JP-A No. 6-87069. Specifically, metal oxide particles are placed in a container equipped with a stirrer such as a hen-shell mixer, and the various silicon-containing compounds described above are added with stirring, and the mixture is brought into contact, preferably in gaseous or spray form. The reaction can be carried out by uniformly mixing and reacting at a high temperature. In the above surface treatment, the amount of the silicon-containing compound to be surface-modified in the component (B) is preferably from 0.01 to 20% by weight, more preferably from 0.1 to 20% by weight, based on the total amount of the component (B). It is from 0.5 to 10% by weight, more preferably from 1 to 8% by weight.

In the present invention, the component (B) that can be particularly preferably used is fumed silica surface-modified with a silicon-containing compound.

The fumed silica is formed by aggregating a plurality of spherical amorphous silica primary particles, and forms an agglomerate (agglomerated particles) having a branched structure. In the agglomerated particles, the agglomeration of the primary particles is caused by hydrogen bonding and van der Waals force. Therefore, the agglomerated particles are broken down in the process of melting and mixing with the resin, but are broken down to the primary particles. Is rarely observed in the resin composition as an aggregate (aggregated particle) having a branched chain structure formed by aggregation of primary particles. The particle size distribution of the aggregated particles in the resin composition is relatively sharp.

Further, the particle surface of the fumes Doshiri mosquito, effective against 3-4 Z nm is ² Sila Roh Lumpur groups are present, surface sila Nord based surface modifying the particle surface with the silicon-containing compound via the It is possible to do it efficiently. Fumed silica surface-modified with a silicon-containing compound is particularly preferable because its surface becomes hydrophobic, dispersing in the resin composition becomes easy, and particle size distribution becomes sharp. „

PCT / JP02 / 13404

33 Humid silica obtained by the dry method has low water absorption because the primary particles are not porous structures but are dense spherical particles, and thus have adverse effects such as hydrolysis of the resin. It is preferable because the influence on the resin during the melt-kneading and molding process is extremely small.

As a scale for judging the porous structure, there is a "pore volume" measured by a nitrogen adsorption method or a mercury intrusion method, but in the present invention, the pore volume is 0.3 m1 Zg or less. Amorphous fume silica is particularly preferred.

The moisture content of the amorphous fumed silica is preferably 5% or less, more preferably 3% or less, further preferably 1% or less, and particularly preferably 0.5% or less. %, Most preferably 0.3% or less.

Specific examples of the component (B) that can be preferably used in the present invention include “Aerosil RY200”, “Aerosil RX200”, and “Aerosil”, which are available from Nippon Aerosil Co., Ltd., Japan. R805, AEROSIL R202, AEROSIL R974J, and AEROSIL200, and the like. The amount of component (B) to be added is component (A) 0.010.5 parts by weight, preferably 0.050.45 parts by weight, more preferably 0.080.4 parts by weight, based on 100 parts by weight. More preferably, 0.10.35 parts by weight, most preferably 0.10.3 parts by weight. If it is less than 0.01 parts by weight, A high flame-retardant effect cannot be obtained, while if it exceeds 0.5 part by weight, the melt stability of the composition, the mechanical properties, the surface appearance of the molded article, and the like tend to decrease.

The aromatic polycarbonate resin composition of the present invention has a branched structure in a mixture containing an aromatic polycarbonate (A), an alkali metal salt of an organic sulfonate (C), and a fluoropolymer (D). The resin composition has a form in which the metal oxide particles (B) having the following are present as randomly dispersed particles. Surprisingly, in the combustion process, the component (B) in the composition is formed into a compact. It is observed that the component (B) is concentrated on the surface to form a surface layer of the component (B).

In the combustion process, the state in which the component (B) is concentrated on the surface of the molded body (formation of the surface layer of the component (B)) can be described, for example, by applying the resin composition of the present invention to an underwriter's laboratory subject. 9 (hereinafter referred to as UL-94 standard.) 20 mm vertical burning for a resin composition test piece with a thickness of 5 mm or less molded for the flame retardancy test described in After performing the test, a scanning probe microscope (SPM) is used to measure the area of the non-carbonized test piece surface that is less than 3 cm from the end of the flame contact side of the test piece after the combustion test. This can be done by observing the surface.

In the above observation method, the component (B) dispersed in the entire observation surface is 1; in a predetermined region of mXl zim, the occupied area of the component (B) in the predetermined region of 1 / xmXl / m is 30% or more, good A resin composition having a content of preferably at least 50%, more preferably at least 70% exhibits a particularly excellent flame retardant effect.

In the aromatic polycarbonate resin composition of the present invention, the formation of the surface layer composed of the component (B) during the combustion process as described above exhibits an excellent flame retardant effect in a thin molded article. This is presumed to be one of the reasons. In other words, it is presumed that the surface layer composed of the component (B) formed in the combustion process exerts a function as a heat insulating layer and a function of controlling diffusion of the combustion gas to the surface.

The component (B) randomly dispersed in the resin composition, which is observed in the aromatic polycarbonate resin composition of the present invention, is concentrated on the surface of the molded body during the burning process, and the component (B) is added to the surface of the molded body from the component (B). The reason why the phenomenon that a surface layer is formed is not clear, but is presumed as follows.

1) During the combustion process, the metal oxide particles (B) having a branched structure present on the surface of the molded product are converted into particles by the radiant heat from the flame, causing the particles to react with each other on the surface of the component (B). It reaggregates via high surface hydroxyl groups and can form a surface layer composed of metal oxide.

2) Due to the shape of the metal oxide particles (B) having a branched structure, a dense surface layer with few gaps can be formed in the combustion process.

3) The average particle size of the metal oxide particles (B) having a branched structure is Nano-size order, high mobility in molten resin 4) In addition, when the surface of the metal oxide particles (B) having a branched structure is coated with a hydrophobic surface treatment agent, The surface energy of the component (B) is small, the metal oxide-air interface interaction is relatively large compared to the metal oxide particle-resin interaction, and the metal oxide particles move toward the air surface side. Surface energy is easily balanced.

The component (C) in the present invention is an alkali metal salt of an organic sulfonic acid, and examples thereof include an alkali metal salt of an aliphatic sulfonic acid and an alkali metal salt of an aromatic sulfonic acid. . Examples of alkali metals include lithium, sodium, potassium, rubidium, and cesium, preferably lithium, sodium, potassium, and most preferably. Alkali metal salts of aliphatic sulfonic acids, which are potassium or potassium, include alkali metal salts of alkanesulfonic acids having 1 to 8 carbon atoms, or alkyl groups of such metal salts of alkaline sulfonic acids. Alkali metal sulfonates, some of which have been substituted with fluorine atoms, and alkali metal perfluoroalkanosulfonates having 1 to 8 carbon atoms can be preferably used. Particularly preferred specific examples include sodium perfluoroethanesulfonic acid salt and potassium perfluorobutanesulfonic acid salt.

Alkali metal salts of aromatic sulfonic acids include monomeric or polymer-like aromatic sulfide sulfonic acids and aromatics Carboxylic acid and ester sulfonic acid, monomeric or polymeric aromatic ether sulfonic acid, aromatic sulfonic acid sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric Or condensates of aromatic sulfonic acids in the form of polymers, sulfonic acids of aromatic ketones, heterocyclic sulfonic acids, sulfonic acids of aromatic sulfoxides, and methylene-type bonds of aromatic sulfonic acids Aromatic sulfonic acid alkali metal salts having at least one aromatic sulfonic acid selected from the group can be mentioned.

As the preferred examples of the above-mentioned monomeric or polymeric alkali metal sulfonate alkali metal sulfonates, diphenylsulfuride-1,4,4,1-disulfonic acid dinatrioxide is a preferred example. And diphenyl sulfide-1,4,4′-dicarium disulfonate.

Preferable examples of the alkali metal sulfonic acid salts of aromatic carboxylic acids and esters include 5-sodium sulfoisulfate, 5-sodium sodium sulfoisophthalate, and the like. And poly (ethylene terephthalate) and poly (sodium sulfonate).

Preferred examples of the above-mentioned metal sulfonic acid alkali metal salt of a monomeric or polymeric aromatic ether include 4-dodecylphenyl ether disulfonate dinadium, poly (2,4) 6 — Dimethyl phenylenoxide) Polysulfonic acid Poly sodium, poly (1,3—phenylenoxide) Poly sodium sulfonate, Poly (1,4—phenylene oxide) Poly sodium sulfonate And poly (2,6-diphenylphenylene oxide) polysulfonate, and poly ((2-fluoro-6-butylbutylphenylene oxide)) polylithium lithium sulfonate.

Preferred examples of the above-mentioned alkali metal sulfonate alkali metal salts include sulfonic acid rims of benzene sulfonate.

Preferred examples of the above-mentioned monomeric or polymeric alkali metal alkali sulfonate include sodium benzenesulfonate, di-palladium p-benzenedisulfonate, and naphthenium. Len-1,6-disulfonic acid dicalium can be mentioned.

Preferred examples of the monomeric or polymeric alkali metal sulfonate sulfonic acid alkali metal salt include sodium diphenylsulfonate-13-sulfonate and sodium diphenylsulfonate-13-sulfone. Examples thereof include potassium acid, diphenylsulfone-33'-dicarboxyl disulfonic acid, and diphenylsulfone-13,4'-dicarium disulfonate. The preferred metal salts of the aromatic ketone sulfonates are, for example,, a, sodium trifluoroacetophenone-14-sodium sulfonate and benzophene. Non-One 3, 3'-disulfonic acid dicadium can be mentioned.

Preferred examples of the above-mentioned alkali metal salts of heterocyclic sulfonic acid include thiophene 1,2,5-dinadium disulfonic acid, thiophene 1,2,5-dicadium disulfonic acid, and benzothiophene. And sodium sulfonate.

Preferred examples of the above-mentioned alkali metal sulfonate alkali metal sulfonate include potassium diphenylsulfoxide 4-sulfonate.

Preferred examples of the condensate of methylene-type bond of the above-mentioned alkali metal salt of aromatic sulfonic acid include a formalin condensate of sodium naphthalene sulfonic acid and sodium anthracene sulfonic acid. An example is a formalin condensate of lithium.

The component (C) has an action of promoting the decarboxylation reaction of the aromatic polycarbonate during combustion with respect to the aromatic polycarbonate of the component (A). However, in the present invention, an excellent flame retardant effect can be obtained by using an extremely small amount of the component (C) due to the synergistic combustion suppressing action of the component (B) and the component (C). This is possible.

By using the component (B) and the component (C) in combination, the decarboxylation reaction of the aromatic polycarbonate can be performed at a lower temperature than when the component (C) is used alone. The progress of the decarboxylation reaction gradually and uniformly throughout the composition can be observed with an optical microscope equipped with a Caro heat stage. In the aromatic polycarbonate resin composition of the present invention, an excellent flame retardant effect can be obtained by using a small amount of the component (C), so that the aromatic polycarbonate resin inherently has heat resistance and heat resistance. Not only is the impact resistance maintained at a high level, but it is also possible to obtain the same melt stability as that of the aromatic polycarbonate as the base resin.

The amount of the component (C) used in the present invention is from 0.0001 to 0.2 part by weight, preferably from 0.01 to 0.1 part by weight, based on 100 parts by weight of the component (A). The amount is 0.18 part by weight, more preferably 0.005 to 0.15 part by weight, particularly preferably 0.01 to 0.1 part by weight. If the component (C) is less than 0.001 part by weight, the flame retardancy of the thin-walled molded article tends to be insufficient, while if it exceeds 0.2 part by weight, the melt stability of the resin composition The component (D) in the present invention, which is insufficient, is a fluoropolymer, for example, a tetrafluoroethylene polymer such as polytetrafluoroethylene, a tetrafluoroethylene / propylene copolymer and the like. It is a perfluoroalkane polymer other than borotetrafluoroethylene, preferably tetrafluoroethylene polymer, and particularly preferably polytetrafluoroethylene.

The component (D) preferably used in the present invention is a fluoropolymer having a fibril-forming ability, and is a fine powdery fluoropolymer or an aqueous disperser of a fluoropolymer. Various forms of fluoropolymer can be used, such as powdered fluoropolymer / acrylonitrile 'styrene copolymer mixture and powdered fluoropolymer / polymethyl methacrylate mixture. .

In the present invention, a powdery fluoropolymer / acrylonitrile / styrene copolymer (AS) mixture or a powdery fluoropolymer / polymethyl methacrylate (PMMA) mixture is used. Can be particularly preferably used. For a mixture of such a powdery fluoropolymer / AS mixture and a thermoplastic resin such as a fluoropolymer ZPMMA mixture, see Japanese Patent Application Laid-Open No. Hei 9-95583 (US Pat. No. 5,804,6). No. 54), Japanese Patent Application Laid-Open No. 11-149912 (corresponding to U.S. Patent No. 6,040,370), Japanese Patent No. 2000-1 Reference can be made to JP-A-43-966, JP-A-2000-299789, and the like, which can be preferably used in the present invention. Examples include “B1 endex 449” manufactured by Charity Chemicals and “Metaprene A-380” manufactured by Mitsubishi Rayon Co., Ltd. of Japan.

In the present invention, the amount of the component (D) is from 0.01 to 0.5 part by weight, preferably from 0.03 to 0.4 part by weight, based on 100 parts by weight of the component (A). Parts, more preferably 0.05 to 0.35 parts by weight, and even more preferably 0.08 to 0.3 parts by weight. PC 碰 3404

If the amount of the component (D) is less than 0.01 part by weight, the effect of preventing the dripping of the burned material in a thin molded article is insufficient. On the other hand, if it exceeds 0.5 part by weight, the surface of the molded article is insufficient. In addition, appearance defects such as silver strikes are likely to occur.

The aromatic polycarbonate resin composition of the present invention may contain at least one kind of additive (E) consisting of a reinforcing material and a filler. The component (E) is used for imparting functions such as rigidity, dimensional stability, and mechanical strength of the resin composition.

The component (E) that can be used in the present invention includes, for example, glass fiber, carbon fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon carbide fiber, aramid fiber, liquid crystal polyester, talc, My strength, creed, wallath tonite, montmorillonite, kaolin, sepiolite, glass flake, glass beads, glass balloon, mil glass, quartz glass, silica, potassium titanate, Examples thereof include silicon carbide, calcium carbonate, magnesium carbonate, graphite, calcium sulfate, and barium sulfate, and one or more selected from these can be used.

As the component (E), among the above, among the above, a small amount selected from the group consisting of glass fiber, carbon fiber tarryk, my strength, wallastone, glass flake, glass beads, glass balloon, quartz glass and silica It is preferable to use at least one kind of glass fiber, carbon fiber, glass flake, glass beads, and glass. It is particularly preferred to use at least one member selected from the group consisting of balloons, quartz glass, and silica.

The pH of the component (E) is from 6 to 10, preferably from 6.5 to 9.5. If the pH is out of this range, the melt stability of the resin composition tends to decrease. In addition, the pH of the component (E) can be measured by a method according to JIS K5101. The component (E) that can be used in the present invention is particularly preferably one whose surface has been treated with a silane coupling agent or the like described in the description of the component (B). When the component (E) is further used, various compounds such as an epoxy compound, a urethane compound, and an acryl compound can be used in combination as a sizing agent. By using the surface-treated component (E), the decomposition of the aromatic polycarbonate (A) can be suppressed, and the adhesion to the resin can be further improved. Functions such as stability and mechanical strength can be favorably imparted.

In the composition of the present invention, at least one selected from the group consisting of glass fibers, carbon fibers, glass flakes, glass beads, glass balloons, quartz glass and silica is used as the component (E). In this case, it is particularly preferable to use an aminosilane-based silane coupling agent and a urethane-based sizing agent.

When glass flakes or a combination of glass fiber and glass flakes are used as the component (E), Preferable for enhancing dimensional stability.

In the present invention, when the component (E) is used, the amount used is 1 to 200 parts by weight, preferably 3 to 100 parts by weight, per 100 parts by weight of the component (A). Parts by weight, more preferably 5 to 50 parts by weight.

In the present invention, by using the component (E), it is possible to increase the rigidity of the aromatic polycarbonate resin composition. The rigidity of the resin composition can be evaluated by the flexural modulus. In the present invention, the flexural modulus of the resin composition measured according to IS 0-178 is preferably from 3,000 to 12,2,000 MPa, more preferably from 3,000 MPa. , 500 to ；; L 0, 000 MPa, particularly preferably 4, 000 to 8, OOOMPa.

In addition, the aromatic polycarbonate resin composition of the present invention may be used to improve the mechanical properties such as melt flowability or impact resistance of the resin composition. The fat may be contained in an amount of 0 to 5 parts by weight, preferably 0 to 3 parts by weight, based on 100 parts by weight of the component (A).

Examples of the thermoplastic resin other than the aromatic polycarbonate include a polystyrene resin, a polyphenylene ether resin, a polyolefin resin, a polyvinyl chloride resin, and a polyamide resin. At least one selected from polyester resins, polyphenylene sulfide resins, polymethacrylate resins, and rubber-modified polymers can be used. Among the above, polystyrene resins and Z or rubber-modifying polymers can be preferably used in the present invention, and polystyrene resins are particularly preferable. A good example is Acrylonitrile 'styrene copolymer resin.

(AS) and polystyrene resin (PS). Particularly preferred examples of the rubber-modified polymer include acrylonitrile-butadiene-styrene copolymer (ABS). Butadiene styrene copolymer (MBS) Methyl methacrylate / butadiene copolymer (MB), methyl methacrylate. Butyl acrylate copolymer (MBA) Methyl methacrylate Butyl acrylate / styrene copolymer (MBAS), acrylonitrile / butyl acrylate-styrene copolymer (AAS), high-impact polystyrene (HIPS), etc. be able to.

Further, the aromatic polycarbonate resin composition of the present invention further contains various additives such as a colorant, a dispersant, a heat stabilizer, a light stabilizer, a lubricant, a release agent, and an antistatic agent. The amount of these components may be generally in the range of 0 to 5 parts by weight based on 100 parts by weight of the component (A).

Next, a method for producing the aromatic polyester resin composition of the present invention will be described.

The production of the aromatic polycarbonate resin composition of the present invention comprises the components (A), (B), (C) and (D), and, in some cases, (E) and / or the other components described above are melt-kneaded using a melt-kneading device such as a Banbury mixer, a singular extruder, a single-screw extruder, or a twin-screw extruder. Although it can be manufactured, twin-screw extruders are particularly suitable for uniformly dispersing the components in the composition and for continuously manufacturing the composition of the present invention.

A particularly preferred production method is that the ratio of the length (L) in the extrusion direction to the extruder screw diameter (D), LZD is 5 to 100, preferably 10 to 70, and more preferably 2 to 100. This is a melt-kneading method using a twin-screw extruder of 0 to 50.

As a method for producing the resin composition of the present invention, for example, each component as a raw material is mixed in advance using a preliminary mixing device such as a tumbler or a re-pump renderer, and then supplied to an extruder to be melt-kneaded. In this case, a method for obtaining the resin composition can be mentioned, but when the component (E) is used, a method for producing the resin composition by side feeding the component (E) from the middle of the extruder is also available. It can be preferably used.

As for the conditions of the melt kneading, for example, when an extruder is used, the cylinder set temperature of the extruder is set to 200 to 400 ° C., preferably 220 to 350 ° C., more preferably 23 to 40 ° C. 0 to 300 ° C., and the number of revolutions of the extruder screw is 50 to 700], preferably 80 to 500 rpm, more preferably 100 to 700 rpm. At 300 rpm, the average residence time of the molten resin in the extruder is 10 to 150 seconds, preferably 20 to: L 00 seconds, and more preferably 30 seconds. Melt kneading is performed for ~ 60 seconds. The temperature of the molten resin is preferably in the range of 250 to 330 ° C, and the melt-kneading is performed while taking care not to give excessive heat to the resin during the kneading. The melt-kneaded resin composition is extruded as a strand from a die attached to the tip of the extruder, and pelletized to obtain a pellet of the resin composition.

In the production method for obtaining the resin composition of the present invention, devolatilization is preferably performed simultaneously with the melt-kneading. Here, “devolatilization” means removing volatile components generated in the melt-kneading process by venting to atmospheric pressure or reducing pressure through a vent port provided in the extruder.

When the devolatilization is carried out under reduced pressure, it is preferably 1 to 5 × 10 ⁴ Pa, more preferably 10 to 4 × 10 ⁴ Pa, and further preferably 100 vacuum devolatilization is carried out at ^{~ 2 X 1 0 4 P a} .

The aromatic polycarbonate resin composition of the present invention can be molded into various products by molding methods such as injection molding, gas assist molding, extrusion molding, blow molding, and compression molding. However, among them, injection molding and gas assist molding are particularly preferable in using the resin composition of the present invention.

Examples of the molded article using the aromatic polyester resin composition of the present invention include computer-related members such as a computer monitor, a mouse, and a keyboard, and a notebook type personal computer. Copiers, fax machines, printers, projectors, portable machines Examples include housings or structural parts for various devices such as instruments, electronic and electrical devices, and precision instruments.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

In Examples and Comparative Examples, aromatic polycarbonate resin compositions were produced using the following components.

1. Component (A): Aromatic polycarbonate

(P C-1)

Bisphenol A-based polycarbonate produced by the melt transesterification method [the repeating unit of the above formula (9) and the above formula

Aromatic polycarbonate composed of (10) heterogeneous bonding units] M w = 21, 600

Phenolic end group ratio = 24%

Hetero bond unit content = 0.08 mol%

The phenolic end group ratio was measured by the NMR method.

The content of the heterogeneous bonding unit was measured by the following method. That is, after dissolving 55 mg of aromatic polycarbonate in 2 ml of tetrahydrofuran, 0.5 ml of 5N potassium hydroxide / methanol solution was added, and The mixture was stirred at room temperature for 2 hours to completely hydrolyze. Thereafter, 0.3 ml of concentrated hydrochloric acid was added, and measurement was performed by reversed-phase liquid chromatography. Reversed-phase liquid chromatography is a UV detector with 991 L-type machine (Waters, USA), Inertsi 1 ODS — 3 column (GL Science, Japan), and a lysing solution. With methanol and 0.1% phosphoric acid Using a mixed solution consisting of a solution, column temperature 25 ° C, methanol / 0.1% phosphoric acid aqueous solution ratio is started from 20/80 to 100/0 The measurement was performed under gradient conditions, and the detection was performed using a UV detector with a wavelength of 300 nm, and quantified based on the extinction coefficient of the standard substance. As the standard substance, a hydroxy compound corresponding to a structure obtained by hydrolyzing a heterogeneous bond unit of the above formula (10) was used. The content of the heterogeneous bond unit was defined as mol% of the heterogeneous bond unit of the formula (10) based on the molar amount of the repeating unit of the formula (9).

(P C-2)

Bisphenol A-based polycarbonate produced by the phosgene method

Mw = 21, 500. The ratio of phenolic end groups = 2%

Heterogeneous binding unit content = not detected.

2. Component (B): metal oxide particles having a branched structure

(Oxide particles-1)

Silicon oxide particles (fumed silica) having a branched structure obtained by a dry method and surface-treated with polydimethylsiloxane (trade name "Aerosil R Y200", manufactured by Nippon Aerosil Co., Ltd.)

(Oxide particles— 2)

Silicon oxide particles having a branched structure obtained by the dry method (Hyumedo silica) (without surface treatment) (Aerosil 200, manufactured by Japan Aerosil Co., Ltd.)

(Oxide particles-1)

Titanium oxide particles having a branched structure obtained by a dry process and surface-treated with octylsilane (trade name “Aerosil T805” manufactured by Nippon Aerosil Co., Ltd.)

3. Component (C): Alkali metal salt of organic sulfonic acid

(C ₄ F ₉ SO 3 K)

Perfluorinated calcium sulfonate (trade name “MegaFack F, 114” manufactured by Dainippon Ink Industries, Ltd. of Japan)

4. Ingredient (D): Fluoropolymer (PTFE / AS)

50/50 (weight ratio) powder mixture of polytetrafluoroethylene (PTFE) and acrylonitrile / styrene copolymer (AS) (GE Specialty Chemicals, USA Brand name "B 1 endex 4 4 9")

5. Additives (E) (reinforcement and / or filler)

(G F)

Japan Nippon Electric Glass Co., Ltd. Chopped strand Product name “T-571”

6. Other ingredients

(1-1 0 7 6)

Octadecyl 3-(3'5-G-t-butyl-4-hydroxyphenyl) Propionate (Hindered phenolic antioxidant manufactured by Chino Specialty Chemicals, Japan) Agent brand name “IRGANOX 1 0 7 6”)

(P-1 6 8)

Tris (2,4-di-t-butylphenyl) phosphite (trade name “IRGAF〇S168”, a phosphite heat stabilizer manufactured by Ciba Specialty Chemicals, Japan) (Release agent)

Japan Penyu Eri Co., Ltd. Pencil Ellis Thitol Tetra Stearate Product name “UNISU Yuichi H476J Example 1

An aromatic polycarbonate resin composition was produced with the composition shown in Table 1. The specific manufacturing method is as follows.

The melt-kneading of each component was performed at a cylinder set temperature of 270 using a twin-screw extruder (PCM-30, L / D = 28, manufactured by Ikekai Iron Works, Japan) as a melt-kneading device. The test was performed under the conditions of a screw rotation speed of 150 rpm and a kneading resin discharge speed of 15 kg Z hr. During the melt kneading, the temperature of the molten resin measured with a thermocouple at the extruder die was 290 ° C.

The raw materials were charged into the twin-screw extruder by pre-blending all the components for 20 minutes using a tumbler and then using a weight feeder to supply the raw materials to the extruder from the supply port. Further, the extruder, the press and out Shi viewed in the direction of the venting port is provided downstream of the feed port, the pressure was reduced devolatilization at 2 XI 0 ⁴ P a via the base emissions collected by filtration. The melt-kneaded resin composition was extruded as a strand from a die, and pelletized to obtain an aromatic polycarbonate resin composition.

The pellets of the resin composition obtained by the above method were dried at 120 ° C. for 5 hours, and evaluated by the following measurement methods. TJP02 / 13404

54

(1) Measurement of average particle size and particle size distribution of inorganic compound particles (B)

An ultra-thin section cut from a pellet of the resin composition was observed with a transmission electron microscope (TEM, manufactured by JEOL Ltd., Japan) and photographed. The average particle diameter (unit: nm) and the ratio of the number of inorganic compound particles present in the particle diameter range of 100 to 200 nm (unit: 100) :%).

The particle diameter of each particle was obtained by calculating the area S of the particle in the above micrograph and using S to obtain (4S / π). · ⁵ is the particle diameter of each particle.

(2) Flame retardancy test

A strip-shaped molded product (thickness: 1.5 mm, 1.20 mm, 1.000 mm, 0.80 mm) for a combustion test was injected into an injection molding machine (Auto Shot 5 manufactured by FANUC, Japan). 0 D), and set at a cylinder set temperature of 290 °: mold set temperature of 80 ° C, and kept for 2 days in an environment of a temperature of 23 ° C and a humidity of 50%. A 20 mm vertical combustion test was performed according to the UL-194 standard.

Classified as V-1 or V-2. (Degree of flame retardancy: V-0>

V-1> V-2)

For some of the compositions, a 500 W vertical burning test was performed using a 200 mm thick strip-shaped compact according to UL-94 standard, and 5 VB Was determined. (3) Heat distortion temperature (HDT) measurement

Using an injection molding machine (Fanuc 50D made by FANUC Japan), test specimens were molded at a cylinder set temperature of 290 ° C and a mold set temperature of 80 ° C. The measurement was carried out at a load of 18.2 MPa according to IS〇-75-1-1. (Unit: C.)

(4) Impact resistance measurement

Using an injection molding machine (50D, a short shot made by FANUC, Japan), the test specimen for measurement was set at a cylinder set temperature of 29 ° C and a mold set temperature of 80 ° C. Was molded and measured with a / inch thick notch according to ASTMD 256. (Unit: J / m),

(5) Flexural modulus measurement

Using an injection molding machine (Auto Shot 50D, manufactured by FANUC, Japan), the cylinder temperature was set at 290 ° C and the mold temperature was set at 80 ° C. A test piece for measurement was molded under the conditions of C, and the measurement was carried out according to IS-1178. (Unit: MPa)

(6) Melt stability measurement

Injection molding machine with cylinder set temperature of 290 ° C (Japan

After holding the molten resin composition in FANUC Auto Shot 50D) for 40 minutes, a 1Z8 inch thick strip was molded at a mold set temperature of 80 ° C. The measurement was performed with a 1 / 8-inch notch according to ASTMD256. (Unit: J / m) The measurement was performed on five test pieces, and the number of brittle fractures was counted. (Unit: out of 5 books) Example 2

An aromatic polyester resin composition was produced in the same manner as in Example 1 except that oxide particles 12 were used. The obtained resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

An aromatic polycarbonate resin composition was produced in the same manner as in Example 1 except that oxide particles 13 were used. The obtained resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.Comparative Examples 1 to 4

A resin composition was produced with the composition shown in Table 1 in the same manner as in Example 1, and various evaluations were made.

Sulfate barium used in Comparative Example 2 (B a S 〇 ₄₎ (Germany zag preparative Leben trade name "ZAKU Topasu") is Ri Oh inorganic compound particles having no branched structure with a grain-like form Does not satisfy the requirement of the component (B) of the present invention.

The granular silica used in Comparative Example 3 (trade name “Nipsi 1E — 75”, manufactured by Nippon Silica Industry Co., Ltd., Japan) is a granular silica having no branching structure. Yes, the component (B) of the present invention Does not meet the requirements of

The granular titanium oxide used in Comparative Example 4 is a rutile type titanium dioxide having no branched structure in a granular form, and does not satisfy the requirement of the component (B) of the present invention.

Table 1 shows the evaluation results.

Examples 4 to 6

Resin compositions were produced in the same manner as in Example 1 using the compositions shown in Table 2, and various evaluations were made. Table 2 shows the results.

In addition, the same method as in Example 4 was used except that the component (C) was changed to potassium perfluorobutanesulfonate (trade name: “RM-65”) manufactured by Miteni, Italy. With respect to the obtained flame-retardant aromatic polycarbonate resin composition, the state of dispersion of metal oxide particles having a branched structure on the surface of the test piece after the flame-retardant test was observed by the following method.

Using an injection molding machine (Fanuc 50D made by FANUC, Japan), the resin was molded by injection molding at a cylinder set temperature of 290 ° C and a mold set temperature of 80 ° C. The composition was formed into a strip specimen for flame retardancy test with a thickness of 1 16 inches, a 20 mm vertical burn test was performed on the test piece, and the branch structure on the test piece surface after the flame retardancy test was performed. The state of dispersion of the metal oxide particles (B) containing was observed. That is, a test in which flame was applied twice for the same test piece for 10 seconds using the specified method using the specified flame flame, and after the second 10 second flame contact was performed, the flame was extinguished. The dispersion state of the metal oxide particles (B) having a branched structure on one surface was observed.

Observation was made using a scanning probe microscope (Seiko Instruments Inc., Japan) in a region where the surface of the non-carbonized specimen within 3 cm from the end of the flame contact side of the specimen after the combustion test was smooth. Using a 300 HV (manufactured by KK) and DF20 as a cantilever, a surface phase contrast image was obtained in the DFM mode (one of the measurement modes set for the scanning probe microscope above). Observed.

The above observations were made on two test pieces. The results are shown in Fig. 1 and Fig. 2 (The specimen in Fig. 1 extinguished itself in 3 seconds after the second 10 second flame contact in the 20 mm vertical combustion test.

(The flame retardancy was determined to be V-0.) The test piece in Fig. 2 self-extinguished 6 seconds after the second 10 second flame contact in the 20 mm vertical flame test (flame retardancy determination). Is V-0). ).

In addition, in a predetermined area of 1 tm × 1 m where the component (B) was dispersed over the entire observation surface, the area occupied by the component (B) in this region was measured. The measurement of the occupied area is based on the SPM surface observation photograph

The area of 1 mx 1 / m was enlarged and printed out on the paper, the occupied portion of the component (B) was cut out, the amount of children was measured, and the occupied area was calculated from the weight ratio (unit: %). Comparative Examples 5 to 9

Resin compositions were produced in the same manner as in Example 1 using the compositions shown in Table 2, and various evaluations were made. Table 2 shows the results. Table 2

Note: (1) In the table, "one" means measurement

(2) The PTFE content of PTFE / AS used as component (D) is 50% by weight.

0213404

62 Example? To 9

An aromatic polycarbonate resin composition was produced with the composition shown in Table 3. The specific manufacturing method is as follows.

The melt-kneading of each component is performed using a twin-screw extruder (ZSK-40MC, L / D = 48, manufactured by Werner & Pfleiderer, Germany) as a melt-kneading device and setting the cylinder temperature. The test was performed at 270 ° C., a screw rotation speed of 100 rpm, and a discharge speed of the kneaded resin of 75 kg / hr. During the melt kneading, the temperature of the molten resin measured with a thermocouple at the die of the extruder was 285 to 295 ° C.

Raw materials are supplied to the twin-screw extruder by pre-blending all components except for component (E) using a tumbler in advance for 20 minutes, and then feeding the extruder using a weight feeder. I put it in my mouth. The component (E) was fed through another feed port provided in the middle stage of the extruder. After supplying the component (E), viewed in the extrusion City direction of extruder venting port is provided downstream of the feed opening for the rhino Dofi de vacuum at 3 XI 0 ⁴ P a through the venting port Devolatilized. The melt-kneaded resin composition was extruded from a die as a strand, and pelletized to produce an aromatic polycarbonate resin composition. After the pellet of the obtained resin composition was dried at 120 ° C. for 5 hours, each measurement was performed. Table 3 shows the results. Comparative Examples 10 and 11

With the compositions shown in Table 3, resin compositions were produced in the same manner as in Example 5, and various evaluations were made. Table 3 shows the results.

Table 3

Note: (1) In the table, "one" indicates that measurement has not been performed.

(2) Used as component (D): PTFE content of PTFE / AS is 50% by weight

As is clear from the comparison between the examples and the comparative examples, the aromatic polycarbonate resin composition of the present invention has excellent melt stability, and at the same time, has a high degree of difficulty even in a thin molded product. Flammable.

Industrial applicability

The flame-retardant aromatic polycarbonate resin composition of the present invention exhibits excellent flame retardancy without using a bromine-based flame retardant or a phosphorus-based flame retardant, and the aromatic polycarbonate is inherently used. It is extremely useful industrially because it exhibits excellent melting stability without impairing its heat resistance and impact resistance.

Claims

The scope of the claims

1. Aromatic polycarbonate (A) 100 parts by weight,

Alkali metal salt of organic sulfonic acid (C) 0.00001

0.2 parts by weight, and

Fluoropolymer (D) 0.01 to 0.5 parts by weight

An aromatic polycarbonate resin composition comprising: the metal oxide particles (B), the aromatic polycarbonate (A), the metal oxide particles (B), and the organic resin; It is dispersed in the mixture of the sulfonic acid alkali metal salt (C),

A flame-retardant aromatic polycarbonate resin composition, comprising:

2. The metal oxide particles (B) having a branched structure are particles of at least one metal oxide selected from silicon oxide, titanium oxide, and aluminum oxide. Aromatic polyphenol resin composition.

3. The aromatic polycarbonate resin composition according to claim 2, wherein the metal oxide particles (B) having a branched structure are silicon oxide particles produced by a dry method.

4. The aromatic polycarbonate according to any one of claims 1 to 3, wherein the surface of the metal oxide particles (B) having a branched structure is modified with a silicon-containing compound. Resin composition.

The aromatic polycarbonate resin composition according to any one of claims 1 to 4, comprising (E) 5 to 200 parts by weight.

6. The additive (E) is characterized in that it is at least one substance selected from the group consisting of glass fibers, carbon fibers, glass flakes, glass beads, glass balloons, quartz glass and silica. The aromatic polycarbonate resin composition according to claim 5, wherein

7. The aromatic polycarbonate according to any one of claims 1 to 6, wherein the aromatic polycarbonate (A) is an aromatic polycarbonate obtained by a transesterification method. Resin composition.